Cedrol ethers



United States Patent 3,373,208 CEDROL ETHERS Jack H. Blumenthal, Oakhurst, N.J., assignor to International Flavors & Fragrances Inc., New York, N.Y., a corporation of New York No Drawing. Filed May 20, 1966, Ser. No. 551,535 5 Claims. (Cl. 260611) This invention relates to aliphatic ethers of cedrol and to processes for preparing same.

Ccdrol is a sesquiterpene alcohol which occurs naturally and is readily available. It has the empirical formula (3 E 0. Its structural formula is:

The invention comprises the novel products as well as the novel processes and steps of processes according to which such products are manufactured, the specific embodiments of which are described hereinafter by way of example, and in accordance with which I know prefer to practice the invention.

I have found in accordance with my invention that the lower aliphatic ethers of cedrol have rich, amber odors which are useful as perfumes which may be prepared by the methods given below.

The cedrol ethers of my invention are various lower aliphatic ethers of cedrol such as the methyl, ethyl, propyl, allyl, butyl and methallyl ethers of cedrol. These materials may be illustrated by the structural formula wherein R is methyl, ethyl, propyl, butyl, allyl or methallyl.

As I now prefer, I carry out my invention for the production of cedrol ethers by reacting an alkali metal derivative of cedrol with an alkyl or alkenyl halide or with a neutral sulfuric acid ester such as dimethyl or diethyl sulfate, or with an'alkyl ester of an aryl sulfonic acid.

The following are examples of the cedrol ethers and methods of preparing same as I now prefer to practice my invention. It is to be understood that these examples are illustrative of the invention, and the invention is not to be considered as restricted thereto except as indicated in the appended claims.

Example I To a refluxing mixture of 575 g. xylene and 164 g. of sodium hydride (54% suspension in mineral oil) was added a solution of 575 g. of cedrol (recrystallized) in 2875 ml. of dry xylene. The mixture was refluxed until gas evolution ceased. To the refluxing mixture was added 253 g. of dimethyl sulfate over a period of minutes. The mixture was refluxed for another seven hours. After cooling, the reaction mass was poured into a solution of 285 g. of water and 100 g. of aqueous sodium hydroxide. The oil layer was separated and washed neutral with water. The solvent was stripped 01f to yield 640 g. of crude cedryl methyl ether. GLC indicated one peak with the absence of the starting alcohol. Fractionation yielded 577 g. of cedryl methyl ether, representing a yield of 94%. Analysis for --OCH found: 13.02%; theory: 13.12.

B.P. 96 C./l mm., 11 1.4957, d 0.9762

This material is useful as a perfume, and has an amberwoody odor.

"ice

Example II To a mixture of 200 g. of dry xylene and 57 g. of sodium hydride (54% suspension) at reflux Was added a solution of 222 g. of recrystallized cedrol in 1000 g. of dry xylene. The reaction mixture was refluxed for two hours, and 169 g. of allyl bromide was dropped in at reflux over 30 minutes. The reaction mixture was refluxed for another three hours, cooled and poured into water. The oil layer was separated and washed with water and the solvent distilled off under vacuum. The residue was rushed-over. The distillate weighed 200 g. and GLC indicated one major and one minor peak (20%). The minor peak had the same retention time as cedrol. yield based on cedrol which reacted.) Fractionation yielded cedryl allyl ether.

B.P. C./0.7 mm., n1 1.4981, d 0.9715

This material is useful as a perfume, and has a woodyamber odor with a fruity nuance.

Example 111 Distillation yielded cedryl propyl ether.

Br. 108 C/mm, n 1.4888, .1 0.9562

This material is useful as a perfume, and has a woodyamber odor with an ionone nuance.

Example IV To a refluxing mixture of 200 ml. of heptane and 50 g. of sodium hydride(54% dispersion) was added a solution of 214 g. of recrystallized cedrol in SOO ml. of heptane over a period of one hour. The reaction mixture was refluxed for another 1.5 hours and 154 g. of diethyl sulfate added over a 45 minute period. After refluxing for another 4 hours, the mixture was cooled and poured into 200 g. of ice and 50 g. of 50% sodium hydroxide solution. The oil layer was separated, washed'once with water and the solvent stripped off. The residue weighed 250 g. and GLC (two peaks) indicated the presence of about 25% of unreacted cedrol. The yield was 75% (based on cedrol which reacted). Fractionation yielded cedryl ethyl ether.

B.P. 114 C./ 1.2 mm, 11 1.4910, d 0.9608

This material is useful as a perfume and has a woodyamber odor.

The following is an example of a perfume formula embodying cedryl methyl ether and producing a perfume The NMR data concerning the above ethers are given below:

Proton count is based on assigning theoretical number of protons to upfield signals. Spectrum was measured 3 in CCL, solution at 60 MHz. on Varian A-60 spectrometer. Chemical shift is expressed in ppm. from TMS, used as an internal standard. Signal multiplicities are expressed as s. (singlet), d. (doublet), t. (triplet), q. (quartet) and m. (multiplet).

CEDRYL METHYL ETHER A (p.p.m.) No. of protons CHz-O- 3.12 (5.) 1- 3.2 0113--0 3.0

S. Gem 1 "{roo 5. 7 CH2C 0.85 1.) 3.2

OH2 110- 2.0-1.26 (m.) 13.4

CEDRYL PROPYL ETHER OHO 3.25 11)-- 1.9 CH3--C-O 1.23 (s.) 2.1 Gem-dimethyl CH1-C'H1- 0 90 (t IIII 1L7 om-c- 0.83 ((1.)

-oH,- H0- 1.95-1.25 15.2

CEDRYL E'IHYL ETHER oHr-oHro- 3.55 (q.) 1.8

orra-c-o 2s.) 3.2

S. G y 8 9 CHr-CHz-Q- 1.08 (t.

CH C 0.84 (d) 3.0

OEDRYL ALLYL ETHER H([)=C 6.25.58(m.) I i 5 0:011; 5.32-4.95 (m.)

=o0H,-0 3.85 (m.) 1.8

CH:- H0 2.0-1.28 (m.) 11.5 10

CH3OO 1.23 (s.)- Gem-dimethyl 1.20 (5.) 8.8

In the above examples sodium hydride may be replaced by sodamide in an inert solvent such as heptane or xylene. The mass. spec. of the cedrol ethers give the following molecular weights: M01. wt. Cedryl methyl ether 236 Cedryl allyl ether 262 V Cedryl ethyl ether 250 I claim:

1. A lower aliphatic ether of cedrol useful as a perfume and having the formula wherein R is selected from the group consisting of methyl, ethyl, propyl, butyl, allyl and methallyl.

2. The compound of claim 1 wherein R is methyl, 3. The compound of claim 1 wherein R is ethyl. 4. The compound of claim 1 wherein R is propyl. 5. The compound of claim 1 wherein R is butyl.

References Cited UNITED STATES PATENTS 2,267,733 12/1941 Hensley 260-6' 32 X OTHER REFERENCES Soap, Perfumery and Cosmetics, vol. 34 '(1961), pp. 743-745.

BERNARD HELFIN, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Pitnt No 3,373,208 March 12 1968 Jack H. Blumenthal It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as ShOWII below:

Column 3, first table, first column, line 4 thereof, for

H d H Tea CH -C same column, third table, second column, line 1 thereof, for "3.55" read 3.35 column 4, in the table, first column,

line 1 thereof, for

I HC=C read H( I=C Signed and sealed this 24th day of June 1969.

(SEAL) Attest:

Edward M. Fletcher, J r.

Attesting Officer WILLIAM E. SCHUYLER, JR.

Commissioner of Patents 

1. A LOWER ALIPHATIC ETHER OF CEDROL USEFUL AS A PERFUME AND HAVING THE FORMULA 